CN110982128A - High-pressure-resistant self-lubricating sealing ring and preparation method thereof - Google Patents
High-pressure-resistant self-lubricating sealing ring and preparation method thereof Download PDFInfo
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- 238000007789 sealing Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 118
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 70
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 55
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 55
- 229920001194 natural rubber Polymers 0.000 claims abstract description 55
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 45
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 39
- YVIGPQSYEAOLAD-UHFFFAOYSA-L disodium;dodecyl phosphate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOP([O-])([O-])=O YVIGPQSYEAOLAD-UHFFFAOYSA-L 0.000 claims abstract description 38
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 23
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 23
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008117 stearic acid Substances 0.000 claims abstract description 23
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 238000003801 milling Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000010992 reflux Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 6
- 230000001050 lubricating effect Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000002041 carbon nanotube Substances 0.000 description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 7
- 229910003865 HfCl4 Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a high-pressure-resistant self-lubricating sealing ring, which comprises the following components in percentage by weight: 80-120 parts of natural rubber, 0.5-4 parts of reinforcing agent, 0.8-3.5 parts of vulcanizing agent, 0.5-1.8 parts of accelerator, 2-6 parts of anti-aging agent, 3-8 parts of zinc oxide and 0.6-1.6 parts of stearic acid. The preparation method comprises the following steps: the single-walled carbon nanotube is treated by strong acid to obtain a functional single-walled carbon nanotube containing hydroxyl and carboxyl, and is modified by trimercapto-s-triazine and dodecyl disodium phosphate to obtain a double-modified single-walled carbon nanotube; finally, the finished product is obtained by open milling and press molding of a plate vulcanizing machine. The invention has the advantages that: the single-walled carbon nanotube has excellent mechanical and lubricating properties, has good dispersibility and compatibility with natural rubber after being modified by trimercapto-s-triazine and disodium dodecyl phosphate, and ensures that the prepared sealing ring has excellent high pressure resistance and self-lubricating properties.
Description
Technical Field
The invention belongs to the technical field of seal ring manufacturing, and particularly relates to a high-pressure-resistant self-lubricating seal ring. The invention also relates to a preparation method of the high-pressure-resistant self-lubricating type sealing ring.
Background
The conventional rubber seal ring has the problems that: the pressure resistance is poor, the product surface static friction coefficient is high, and the like, so the service life is short, the sealing ring needs to be frequently replaced, time and labor are wasted, and the resource waste is also caused. Aiming at the problems of poor pressure resistance and changeability of the rubber sealing ring, a high-strength material is generally added; the static friction coefficient of the surface of the sealing ring is changed, and a lubricant is added into a sealing material under the normal condition, but the static friction coefficient can be reduced, but the tensile strength and elasticity of the material are also reduced, the deformation coefficient is increased, and the service life of the sealing ring is directly influenced.
The carbon nano tube, especially the single-layer wall carbon nano tube with an ideal structure, has good mechanical properties including highest specific strength, good toughness and the like, and can be made into a composite material by other materials, so that the composite material can show good strength, elasticity, fatigue resistance and isotropy, and the performance of the composite material is greatly improved. The carbon nano tube has extremely high surface energy, so that the carbon nano tube is easy to agglomerate, the carbon nano tube is unevenly dispersed in a rubber matrix, and the problem is more obvious particularly when the carbon nano tube is blended by a mechanical method. In the existing preparation technology of the carbon nanotube/polymer composite material, the carbon nanotube is mostly dispersed in a liquid phase environment, even if the dispersion is realized by a solid phase mode, the consumption of the carbon nanotube is low, the strength of the obtained composite material is limited, and the composite material is not applied to certain high-pressure environments.
Disclosure of Invention
The invention provides a formula of a rubber sealing ring with remarkable high-pressure resistance and self-lubricating function and a preparation method thereof, aiming at overcoming the defects in the prior art.
The invention provides a formula of a high-pressure-resistant self-lubricating sealing ring, which comprises the following components in parts by weight: 80-120 parts of natural rubber, 0.5-4 parts of reinforcing agent, 0.8-3.5 parts of vulcanizing agent, 0.5-1.8 parts of accelerator, 2-6 parts of anti-aging agent, 3-8 parts of zinc oxide and 0.6-1.6 parts of stearic acid.
The reinforcing agent is a single-walled carbon nanotube modified by trimercapto-s-triazine and dodecyl disodium phosphate.
Specifically, the feed comprises the following components in parts by mass: 104 parts of natural rubber, 3.1 parts of reinforcing agent, 1.9 parts of vulcanizing agent, 1.5 parts of accelerator, 4.8 parts of anti-aging agent, 6 parts of zinc oxide and 1.2 parts of stearic acid.
The preparation of the single-walled carbon nanotube modified by trimercapto-s-triazine and dodecyl disodium phosphate comprises the following steps:
step 1: adding 50g of single-walled carbon nanotube into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, repeating the operation, washing the acidified single-walled carbon nanotube with deionized water and ethanol for 3 times respectively, separating by using a centrifugal machine, and carrying out vacuum drying at 100 ℃ for 24h to obtain the functionalized single-walled carbon nanotube containing hydroxyl and carboxyl;
step 2: adding 0.5-3g of the functionalized single-walled carbon nanotube prepared in the step 1 and 0.05-0.2g of trimercapto-s-triazine into 500ml of toluene solvent4Performing ultrasonic reflux for 24 hours under the catalysis of (THF), filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to prepare the single-walled carbon nanotube containing trimercapto-s-triazine;
and step 3: and (3) adding 0.5-4.5g of the single-walled carbon nanotube containing trimercapto-s-triazine prepared in the step (2) and 0.5-4.5g of disodium dodecyl phosphate into 500ml of sodium hydroxide aqueous solution with the mass fraction of 1%, and performing ultrasonic filtration at 40 ℃ for 24h, washing and drying to obtain the single-walled carbon nanotube modified by trimercapto-s-triazine and disodium dodecyl phosphate.
The mass portion ratio of the natural rubber to the reinforcing agent is 100: 2.75.
the invention also provides a preparation method of the high-pressure-resistant self-lubricating sealing ring, which is characterized by comprising the following steps of:
step 1: adding 50g of single-walled carbon nanotubes into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, and repeating the operation; washing the acidified single-walled carbon nanotubes with deionized water and ethanol for 3 times respectively, separating by a centrifuge, and vacuum-drying at 100 ℃ for 24 hours to obtain the functionalized single-walled carbon nanotubes containing hydroxyl and carboxyl;
step 2: adding 0.5-3g of the functionalized single-walled carbon nanotube prepared in the step 1 and 0.05-0 g of trimercapto-s-triazine into 500ml of toluene solvent.2gHfCl4Performing ultrasonic reflux for 24 hours under the catalysis of (THF), filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to prepare the single-walled carbon nanotube containing trimercapto-s-triazine;
and step 3: adding 0.5-4.5g of the single-walled carbon nanotube containing trimercapto-s-triazine prepared in the step 2 and 0.5-4.5g of dodecyl disodium phosphate into 500ml of sodium hydroxide aqueous solution with the mass fraction of 1%, and performing ultrasonic filtration for 24 hours at 40 ℃ to wash and dry to obtain the trimercapto-s-triazine and dodecyl disodium phosphate modified single-walled carbon nanotube;
and 4, step 4: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and preparing a finished product on a flat plate vulcanizing machine by a mould pressing forming method at 120 ℃ and 6 MPa.
Compared with the prior art, the high-pressure-resistant self-lubricating sealing ring provided by the invention contains natural rubber which is an excellent elastomer and is very suitable for manufacturing the sealing ring; the single-walled carbon nanotube with an ideal structure has good mechanical property, is a solid lubricant as graphite, and has excellent lubricating property; after the trimercapto-s-triazine and the dodecyl disodium phosphate are modified, the introduced trimercapto-s-triazine increases the cross-linking and fusing capacity of the single-walled carbon nanotube with natural rubber in the vulcanization process; the introduced dodecane is a direct alkane which is similar to the chemical structure of natural rubber, can increase the compatibility of the single-walled carbon nanotube and the natural rubber, simultaneously reduces the surface energy of the single-walled carbon nanotube and improves the dispersibility. The mutual influence of the two substances synergistically promotes the uniform dispersion of the single-walled carbon nanotubes in the natural rubber and simultaneously improves the fusion capacity of the single-walled carbon nanotubes and the natural rubber, so that the use amount of the modified single-walled carbon nanotubes is obviously increased to reach 2.75% of the mass of the natural rubber, and the mechanical property and the wear resistance of the natural rubber are greatly improved. Therefore, the sealing ring added with the single-walled carbon nanotube modified by trimercapto-s-triazine and disodium dodecyl phosphate has high pressure resistance and self-lubricating effect.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
110 parts of natural rubber, 2.6 parts of reinforcing agent, 1.9 parts of vulcanizing agent, 1.4 parts of accelerator, 5 parts of anti-aging agent, 7 parts of zinc oxide and 1.4 parts of stearic acid. The vulcanizing agent is sulfur, the accelerator is DM, and the anti-aging agent is anti-aging agent 6 PPD.
Step 1: adding 50g of single-walled carbon nanotubes into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, and repeating the operation. And (3) washing the acidified single-walled carbon nanotubes with deionized water and ethanol for 3 times respectively, separating by using a centrifugal machine, and performing vacuum drying at 100 ℃ for 24 hours to obtain the functionalized single-walled carbon nanotubes containing hydroxyl and carboxyl.
Step 2: adding 3g of the functionalized single-walled carbon nanotube prepared in the step 1 and trimercapto-s-triazine into 500ml of toluene solvent and adding 0.2g of HfCl4And (THF) catalyzing, performing ultrasonic reflux for 24h, filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to obtain the single-walled carbon nanotube containing trimercapto-s-triazine.
And step 3: and (3) adding 4.5g of the single-walled carbon nanotube containing trimercapto-s-triazine prepared in the step (2) and 4.5g of disodium dodecyl phosphate into 500ml of a sodium hydroxide aqueous solution with the mass fraction of 1%, and performing ultrasonic filtration at 40 ℃ for 24h, washing and drying to obtain the trimercapto-s-triazine and disodium dodecyl phosphate modified single-walled carbon nanotube.
And 4, step 4: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and then pressing and molding on a flat plate vulcanizing machine at 120 ℃ and 6MPa to prepare a finished product.
Example 2
80 parts of natural rubber, 0.5 part of reinforcing agent, 0.8 part of vulcanizing agent, 0.5 part of accelerator, 2 parts of anti-aging agent, 3 parts of zinc oxide and 0.6 part of stearic acid. The vulcanizing agent is sulfur, the accelerator is DM, and the anti-aging agent is anti-aging agent 6 PPD.
Step 1: adding 50g of single-walled carbon nanotubes into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, and repeating the operation. And (3) washing the acidified single-walled carbon nanotubes with deionized water and ethanol for 3 times respectively, separating by using a centrifugal machine, and performing vacuum drying at 100 ℃ for 24 hours to obtain the functionalized single-walled carbon nanotubes containing hydroxyl and carboxyl.
Step 2: adding 0.5g of the functionalized single-walled carbon nanotube prepared in the step 1 and 0.01g of trimercapto-s-triazine into 500ml of toluene solvent in 0.01g of HfCl4And (THF) catalyzing, performing ultrasonic reflux for 24h, filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to obtain the single-walled carbon nanotube containing trimercapto-s-triazine.
And step 3: and (3) adding 0.5g of the single-walled carbon nanotube containing trimercapto-s-triazine prepared in the step (2) and 0.5g of disodium dodecyl phosphate into 500ml of a sodium hydroxide aqueous solution with the mass fraction of 1%, and performing ultrasonic filtration at 40 ℃ for 24h, washing and drying to obtain the trimercapto-s-triazine and disodium dodecyl phosphate modified single-walled carbon nanotube.
And 4, step 4: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and then pressing and molding on a flat plate vulcanizing machine at 120 ℃ and 6MPa to prepare a finished product.
Example 3
120 parts of natural rubber, 4 parts of reinforcing agent, 3.5 parts of vulcanizing agent, 1.8 parts of accelerator, 6 parts of anti-aging agent, 8 parts of zinc oxide and 1.6 parts of stearic acid. The vulcanizing agent is sulfur, the accelerator is DM, and the anti-aging agent is anti-aging agent 6 PPD.
Step 1: adding 50g of single-walled carbon nanotubes into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, and repeating the operation. And (3) washing the acidified single-walled carbon nanotubes with deionized water and ethanol for 3 times respectively, separating by using a centrifugal machine, and performing vacuum drying at 100 ℃ for 24 hours to obtain the functionalized single-walled carbon nanotubes containing hydroxyl and carboxyl.
Step 2: adding 1.5g of the functionalized single-walled carbon nanotube prepared in the step 1 and trimercapto-s-triazine into 500ml of toluene solvent and adding 0.03g of HfCl4And (THF) catalyzing, performing ultrasonic reflux for 24h, filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to obtain the single-walled carbon nanotube containing trimercapto-s-triazine.
And step 3: and (3) adding 2.75g of the single-walled carbon nanotube containing trimercapto-s-triazine prepared in the step (2) and 2.75g of disodium dodecyl phosphate into 500ml of a sodium hydroxide aqueous solution with the mass fraction of 1%, and performing ultrasonic filtration at 40 ℃ for 24h, washing and drying to obtain the trimercapto-s-triazine and disodium dodecyl phosphate modified single-walled carbon nanotube.
And 4, step 4: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and then pressing and molding on a flat plate vulcanizing machine at 120 ℃ and 6MPa to prepare a finished product.
Example 4
90 parts of natural rubber, 1.2 parts of reinforcing agent, 1.3 parts of vulcanizing agent, 0.8 part of accelerator, 2.9 parts of anti-aging agent, 4 parts of zinc oxide and 0.8 part of stearic acid. The vulcanizing agent is sulfur, the accelerator is DM, and the anti-aging agent is anti-aging agent 6 PPD.
Step 1: adding 50g of single-walled carbon nanotubes into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, and repeating the operation. And (3) washing the acidified single-walled carbon nanotubes with deionized water and ethanol for 3 times respectively, separating by using a centrifugal machine, and performing vacuum drying at 100 ℃ for 24 hours to obtain the functionalized single-walled carbon nanotubes containing hydroxyl and carboxyl.
Step 2: adding 2.5g of the functionalized single-walled carbon nanotube prepared in the step 1 and trimercapto-s-triazine into 500ml of toluene solvent and adding 0.13g of HfCl4Performing ultrasonic reflux for 24 hours under the catalysis of (THF), filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to obtain the product containing trimercaptoS-triazine based single-walled carbon nanotubes.
And step 3: and (3) adding 4.5g of the single-walled carbon nanotube containing trimercapto-s-triazine prepared in the step (2) and 4.5g of disodium dodecyl phosphate into 500ml of a sodium hydroxide aqueous solution with the mass fraction of 1%, and performing ultrasonic filtration at 40 ℃ for 24h, washing and drying to obtain the trimercapto-s-triazine and disodium dodecyl phosphate modified single-walled carbon nanotube.
And 4, step 4: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and then pressing and molding on a flat plate vulcanizing machine at 120 ℃ and 6MPa to prepare a finished product.
Example 5
100 parts of natural rubber, 1.9 parts of reinforcing agent, 1.9 parts of vulcanizing agent, 1.1 parts of accelerator, 3.9 parts of anti-aging agent, 5 parts of zinc oxide and 1 part of stearic acid. The vulcanizing agent is sulfur, the accelerator is DM, and the anti-aging agent is anti-aging agent 6 PPD.
Step 1: adding 50g of single-walled carbon nanotubes into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, and repeating the operation. And (3) washing the acidified single-walled carbon nanotubes with deionized water and ethanol for 3 times respectively, separating by using a centrifugal machine, and performing vacuum drying at 100 ℃ for 24 hours to obtain the functionalized single-walled carbon nanotubes containing hydroxyl and carboxyl.
Step 2: adding 2g of the functionalized single-walled carbon nanotube prepared in the step 1 and trimercapto-s-triazine into 500ml of toluene solvent and adding 0.1g of HfCl4And (THF) catalyzing, performing ultrasonic reflux for 24h, filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to obtain the single-walled carbon nanotube containing trimercapto-s-triazine.
And step 3: and (3) adding 3.4g of the single-walled carbon nanotube containing trimercapto-s-triazine prepared in the step (2) and 3 ml of disodium dodecyl phosphate into 500ml of sodium hydroxide aqueous solution with the mass fraction of 1%, and performing ultrasonic filtration at 40 ℃ for 24h, washing and drying to obtain the trimercapto-s-triazine and disodium dodecyl phosphate modified single-walled carbon nanotube.
And 4, step 4: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and then pressing and molding on a flat plate vulcanizing machine at 120 ℃ and 6MPa to prepare a finished product.
TABLE 1 performance of seal rings in different examples
| Sample (I) | Compressive strength (MPa) | Coefficient of static friction |
| Example 1 | 56.42 | 0.19 |
| Example 2 | 31.44 | 0.39 |
| Example 3 | 52.03 | 0.23 |
| Example 4 | 45.38 | 0.28 |
| Example 5 | 48.16 | 0.25 |
Comparative example 1
110 parts of natural rubber, 2.6 parts of reinforcing agent, 1.9 parts of vulcanizing agent, 1.4 parts of accelerator, 5 parts of anti-aging agent, 7 parts of zinc oxide and 1.4 parts of stearic acid.
The reinforcing agent is a single-walled carbon nanotube, the vulcanizing agent is sulfur, the accelerator is DM, and the anti-aging agent is anti-aging agent 6 PPD.
The preparation method comprises the following steps: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and preparing a finished product on a flat plate vulcanizing machine by a mould pressing forming method at 120 ℃ and 6 MPa.
In the comparative example, the natural rubber and other components are unchanged in parts by mass, the performance of the sealing ring prepared by changing the parts by mass of the reinforcing agent is different, and experimental data are as follows:
TABLE 2 sealing ring performance of different mass ratios of natural rubber and reinforcing agent in comparative example 1
| Natural rubber: reinforcing agent | Compressive strength (MPa) | Coefficient of static friction |
| 100：0.5 | 9.32 | 0.59 |
| 100：0.6 | 8.27 | 0.64 |
| 100：0.7 | 7.55 | 0.69 |
| 100：0.8 | 6.63 | 0.72 |
| 100：0.9 | 5.15 | 0.75 |
The unmodified single-walled carbon nanotube is used in a small amount in rubber due to poor dispersibility, and the performance of a sealing ring prepared from the single-walled carbon nanotube is poor.
Comparative example 2
110 parts of natural rubber, 2.6 parts of reinforcing agent, 1.9 parts of vulcanizing agent, 1.4 parts of accelerator, 5 parts of anti-aging agent, 7 parts of zinc oxide and 1.4 parts of stearic acid.
The reinforcing agent is a single-walled carbon nanotube modified by trimercapto-s-triazine, the vulcanizing agent is sulfur, the accelerator is DM, and the anti-aging agent is anti-aging agent 6 PPD.
Step 1: adding 50g of single-walled carbon nanotubes into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, and repeating the operation. And (3) washing the acidified single-walled carbon nanotubes with deionized water and ethanol for 3 times respectively, separating by using a centrifugal machine, and performing vacuum drying at 100 ℃ for 24 hours to obtain the functionalized single-walled carbon nanotubes containing hydroxyl and carboxyl.
Step 2: adding 3g of the functionalized single-walled carbon nanotube prepared in the step 1 and trimercapto-s-triazine into 500ml of toluene solvent and adding 0.05-0.2g of HfCl4And (THF) catalyzing, performing ultrasonic reflux for 24h, filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to obtain the single-walled carbon nanotube containing trimercapto-s-triazine.
And step 3: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and preparing a finished product on a flat plate vulcanizing machine by a mould pressing forming method at 120 ℃ and 6 MPa.
In the comparative example, the natural rubber and other components are unchanged in parts by mass, the performance of the sealing ring prepared by changing the parts by mass of the reinforcing agent is different, and experimental data are as follows:
TABLE 3 performance of seal rings of comparative example 2 with different mass ratios of natural rubber and reinforcing agent
The optimal using amount of the single-walled carbon nanotube modified by trimercapto-s-triazine is 2% of the mass of the natural rubber, and when the using amount is more than 2%, the aggregation of the single-walled carbon nanotube can be caused to generate adverse effects.
Comparative example 3
110 parts of natural rubber, 2.6 parts of reinforcing agent, 1.9 parts of vulcanizing agent, 1.4 parts of accelerator, 5 parts of anti-aging agent, 7 parts of zinc oxide and 1.4 parts of stearic acid.
The reinforcing agent is a single-walled carbon nanotube modified by disodium dodecyl phosphate, the vulcanizing agent is sulfur, the accelerator is DM, and the anti-aging agent is anti-aging agent 6 PPD.
Step 1: adding 50g of single-walled carbon nanotubes into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, and repeating the operation. And (3) washing the acidified single-walled carbon nanotubes with deionized water and ethanol for 3 times respectively, separating by using a centrifugal machine, and performing vacuum drying at 100 ℃ for 24 hours to obtain the functionalized single-walled carbon nanotubes containing hydroxyl and carboxyl.
Step 2: and (2) adding 4.5g of the functionalized single-walled carbon nanotube prepared in the step (1) and 4.5g of disodium dodecyl phosphate into 500ml of a 1% sodium hydroxide aqueous solution, and performing ultrasonic filtration at 40 ℃ for 24 hours, washing and drying to obtain the disodium dodecyl phosphate modified single-walled carbon nanotube.
And step 3: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and preparing a finished product on a flat plate vulcanizing machine by a mould pressing forming method at 120 ℃ and 6 MPa.
In the comparative example, the natural rubber and other components are unchanged in parts by mass, the performance of the sealing ring prepared by changing the parts by mass of the reinforcing agent is different, and experimental data are as follows:
TABLE 4 sealing ring performance of different mass ratios of natural rubber and reinforcing agent in comparative example 3
The optimal dosage of the single-walled carbon nanotube modified by the disodium dodecyl phosphate is 2 percent of the mass of the natural rubber, and when the dosage is more than 2 percent, the single-walled carbon nanotube can be aggregated to generate adverse effects.
On the basis that the natural rubber and other components in the formula in example 1 are not changed in parts by mass, the performance of the sealing ring prepared by only changing the mass of the reinforcing agent is different, and experimental data are as follows:
TABLE 5 sealing ring performance of different natural rubber and reinforcing agent mass ratios in example 1
| Natural rubber: reinforcing agent | Compressive strength (MPa) | Coefficient of static friction |
| 100：0.50 | 30.32 | 0.40 |
| 100：1.25 | 44.51 | 0.29 |
| 100：2.00 | 50.63 | 0.24 |
| 100：2.75 | 59.80 | 0.18 |
| 100：3.50 | 50.15 | 0.24 |
The rubber comprises the following components in parts by mass: reinforcing agent 100: 2.75, the natural rubber and the reinforcing agent have the best synergistic effect under the interaction, the natural rubber has the best dispersion and fusion capability, and the natural rubber has the best compression resistance and the lowest static friction coefficient. Too high reinforcing agent dosage can lead to uneven dispersion and aggregation of the reinforcing agent, reduce crosslinking density, cause the rubber matrix to easily form cavitation effect under the action of external force and reduce compression resistance and self-lubricating capacity. The dispersing ability of the single-walled carbon nanotube double-modified by trimercapto-s-triazine and dodecane in natural rubber is obviously improved, and the using amount of the single-walled carbon nanotube can be increased to 2.75% of the quality of the natural rubber.
It was determined that 1g of single-walled carbon nanotubes reacted with up to 0.06g of trimercapto-s-triazine when reacted with trimercapto-s-triazine alone. When reacted with disodium dodecyl phosphate alone, 1g of single-walled carbon nanotubes was reacted with up to 0.09g of disodium dodecyl phosphate.
In example 1, the mass parts of the natural rubber and other components are unchanged, the mass part of the reinforcing agent is adjusted to be 2.75% of the mass of the natural rubber, the influence of the change of the amounts of trimercapto-s-triazine and disodium dodecyl phosphate on the performance of the sealing ring in the preparation process of the modified single-walled carbon nanotube is examined, and the experimental data are as follows:
TABLE 6 sealing ring performance of trimercapto-s-triazine and disodium dodecyl phosphate at different dosages
From the experimental data, the compression resistance and the self-lubricating capacity of the sealing ring prepared from the modified single-walled carbon nanotube and the natural rubber are increased along with the increase of the using amount of trimercapto-s-triazine or disodium dodecyl phosphate in the modified single-walled carbon nanotube; in the preparation process of the modified single-walled carbon nanotube, the performance of the sealing ring is best when the using amounts of trimercapto-s-triazine and disodium dodecyl phosphate are not the maximum, but when the mass parts are as follows: trimercapto-s-triazine: when the disodium dodecyl phosphate is 1:0.05:0.08, the compression resistance and the self-lubricating performance of the sealing ring are optimal, and the synergic dispersion and the compatibility effect with natural rubber of trimercapto-s-triazine and dodecane introduced into the modified single-walled carbon nanotube are best under the proportion.
Claims (6)
1. The high-pressure-resistant self-lubricating sealing ring is characterized by comprising the following components in parts by mass: 80-120 parts of natural rubber, 0.5-4 parts of reinforcing agent, 0.8-3.5 parts of vulcanizing agent, 0.5-1.8 parts of accelerator, 2-6 parts of anti-aging agent, 3-8 parts of zinc oxide and 0.6-1.6 parts of stearic acid;
the reinforcing agent is a single-walled carbon nanotube modified by trimercapto-s-triazine and dodecyl disodium phosphate.
2. The high pressure resistant self-lubricating seal ring according to claim 1,
the paint comprises the following components in parts by mass: 104 parts of natural rubber, 3.1 parts of reinforcing agent, 1.9 parts of vulcanizing agent, 1.5 parts of accelerator, 4.8 parts of anti-aging agent, 6 parts of zinc oxide and 1.2 parts of stearic acid.
3. The high pressure resistant self-lubricating type sealing ring according to claim 1 or 2, wherein the preparation of the single-walled carbon nanotube modified by trimercapto-s-triazine and disodium dodecyl phosphate comprises the following steps:
step 1: adding 50g of single-walled carbon nanotube into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, repeating the operation, washing the acidified single-walled carbon nanotube with deionized water and ethanol for 3 times respectively, separating by using a centrifugal machine, and carrying out vacuum drying at 100 ℃ for 24h to obtain the functionalized single-walled carbon nanotube containing hydroxyl and carboxyl;
step 2: adding 0.5-3g of the functionalized single-walled carbon nanotube prepared in the step 1 and 0.05-0.2g of trimercapto-s-triazine into 500ml of toluene solvent4Performing ultrasonic reflux for 24 hours under the catalysis of (THF), filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to prepare the single-walled carbon nanotube containing trimercapto-s-triazine;
and step 3: and (3) adding 0.5-4.5g of the single-walled carbon nanotube containing trimercapto-s-triazine prepared in the step (2) and 0.5-4.5g of disodium dodecyl phosphate into 500ml of sodium hydroxide aqueous solution with the mass fraction of 1%, and performing ultrasonic filtration at 40 ℃ for 24h, washing and drying to obtain the single-walled carbon nanotube modified by trimercapto-s-triazine and disodium dodecyl phosphate.
4. The high-pressure-resistant self-lubricating sealing ring according to claim 3, wherein the mass part ratio of the natural rubber to the reinforcing agent is 100: 2.75.
5. the high pressure resistant self-lubricating type seal ring according to claim 3, wherein in the step, the mass ratio of the single-walled carbon nanotube, the trimercapto-s-triazine and the disodium dodecyl phosphate is 1:0.05: 0.08.
6. the method for preparing a high pressure resistant self-lubricating seal ring according to claim 1 or 2, characterized by comprising the following steps:
step 1: adding 50g of single-walled carbon nanotubes into 500ml of concentrated nitric acid with the mass fraction of 68%, ultrasonically dispersing for 1h, then refluxing for 2h under stirring at 120 ℃, filtering the obtained suspension, and repeating the operation; washing the acidified single-walled carbon nanotubes with deionized water and ethanol for 3 times respectively, separating by a centrifuge, and vacuum-drying at 100 ℃ for 24 hours to obtain the functionalized single-walled carbon nanotubes containing hydroxyl and carboxyl;
step 2: adding 0.5-3g of the functionalized single-walled carbon nanotube prepared in the step 1 and 0.05-0.2g of trimercapto-s-triazine into 500ml of toluene solvent4Performing ultrasonic reflux for 24 hours under the catalysis of (THF), filtering, washing and drying, and reacting carboxyl of the functionalized single-walled carbon nanotube with trimercapto-s-triazine to prepare the single-walled carbon nanotube containing trimercapto-s-triazine;
and step 3: adding 0.5-4.5g of the single-walled carbon nanotube containing trimercapto-s-triazine prepared in the step 2 and 0.5-4.5g of dodecyl disodium phosphate into 500ml of sodium hydroxide aqueous solution with the mass fraction of 1%, and performing ultrasonic filtration for 24 hours at 40 ℃ to wash and dry to obtain the trimercapto-s-triazine and dodecyl disodium phosphate modified single-walled carbon nanotube;
and 4, step 4: cutting natural rubber into proper size, sequentially adding a reinforcing agent, a vulcanizing agent, an anti-aging agent, an accelerator, zinc oxide and stearic acid into an open mill at room temperature, open milling for 2h, and preparing a finished product on a flat plate vulcanizing machine by a mould pressing forming method at 120 ℃ and 6 MPa.
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